Synthesis And Properties Of The Bis-porphyrins And Metal Complexes With Different Peripheral Substituents

In recent years porphyrin and its derivatives have been widely used in simulatephotosynthesis systems, photodynamic therapy, sensors, self-assembly because oftheir special structure and properties. The porphyrins have been concerned inbiomedicine, biochemistry, medical chemistry and new energy, especially to thebinary, ternary and multiple porphyrins combination with bioactive substances. Now,more and more attention has been given to the porphyrins with different peripheralsubstituents, for improve molecular characters.We designed three kinds of bis-porphyrins with different peripheral substituents,The10,15,20-triphenyl porphyrin Dimer was synthesized with (e)-2-butenedioyldichlorid as a bridge-linked reagent (DP), The10,15,20-tri(p-methoxyphenyl)porphyrin Dimer was synthesized with (e)-2-butenedioyl dichlorid as a bridge-linkedreagent (DP1), The10,15,20-tri(p-chlorophenyl) porphyrin Dimer was synthesizedwith (e)-2-butenedioyl dichlorid as a bridge-linked reagent (DP2). We also synthesizedtheir Zn, Cu, Co, Mn complexes. All of them have been characterized, reseached, andexplored the different substituents electronic effect on the nature of porphyrins.Synthsis route of the compounds: All of them have been synthesized and characterized by IR, MS, elemental analysis,NMR and UV-Vis spectroscopy.From the fluorescence spectra, the substitents effects have great influences in thefluorescence quantum yield of porphyrin molecules and the intensity of fluorescence:the electron-withdrawing groups makes it decrease and the electron-donating groupsmakes it increase. The Fluorescence will be weakened or even extinguished after theformation of metal complexes.Raman spectra show the different peripheral substituents have a great influence onthe skeletal vibration of porphyrin and also influence the vibration of the benzene ring.The plane of the porphyrin molecules was changed following the formation of metalcomplexes.In the SPV spectra: similar to the UV-Vis spectra, the different peripheralsubstituents have little influence in SPV result. The porphyrins can be used assemiconductor.